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Remarkable lowering in the synthesis temperature of LiMn2O4 from citrate solution-gel synthesis facilitated by Ethanol


LiMn2O4 (LMO) is interesting in view of energy storage applications as it’s a cathode for lithium ion batteries(LIB), which contains no rare or toxic or expansive elements, while it provides a high theoretical capacity (148 mAh/g) at a reasonable voltage (4V region), higher thermal stability compared to cobalt based cathodes and has a good rechargeability and cycling stability due to its spinel structure. Low temperature synthesis routes for cathode materials are currently gaining attention, in order to decrease the ecologic footprint of the final LIB. Here, the crystallization temperature of LMO by a citrate based solution-gel synthesis was significantly lowered, to as low as 250°C by the addition of ethanol to the precursor. The role of the ethanol in this synthesis process was explored. It was found to lead to a considerable increase in the oxidation rate of the redox couple Mn2+/Mn3+, a lowering of the precursor decomposition temperature by 200°C, besides a drastic decrease in crystallization temperature (reaching 250˚C). Moreover, the main cause was identified to be an esterification reaction of ethanol with the carboxylic acid in the precursor complexes, taking place before the oxide formation. The insights obtained strengthen the knowledge on citrato-Mn2+/Mn3+ complexes present in aqueous solution-gel synthesis routes and are relevant for the preparation of various manganese containing oxides. Moreover, the precursor developed opens up a new possibility for low temperature synthesis of LMO powders and thin films for application in LIB. In case of thin film batteries, the low temperature processing provides compatibility with other materials in the thin film battery stack, avoiding undesired oxidations or interfacial reactions.

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Publication details

The article was received on 21 Aug 2017, accepted on 28 Sep 2017 and first published on 29 Sep 2017

Article type: Paper
DOI: 10.1039/C7DT03100A
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Remarkable lowering in the synthesis temperature of LiMn2O4 from citrate solution-gel synthesis facilitated by Ethanol

    G. Maino, R. Carleer, W. Marchal, G. Bonneux, A. Hardy and M. K. Van Bael, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT03100A

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